Trisaminopyridines and method of preparation by reaction of diamino-2-chloro pyridinium salt and organic amine

ABSTRACT

Trisaminopyridines of the formula ##STR1## are prepared by reacting a pyridinium salt of the formula ##STR2## with an organic amine having the formula R 3  NH 2  at a temperature of 110° C. to 130° C.; 
     in which 
     X is --CN, --CONQ 1  Q 2  or --COOQ 3  ; 
     R is substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or aryl; 
     R 1  is substituted or unsubstituted alkyl, aralkyl or aryl; 
     Q 1  and Q 2  independently of one another are hydrogen, alkyl, cycloalkyl, aralkyl or aryl; or conjointly with the nitrogen atom form a 5-membered or 6-membered heterocyclic structure; and 
     Q 3  is alkyl or aralkyl. 
     Where X is --CONQ 1  Q 2  or --COOQ 3 , the --CN group in the starting pyridinium salt is subsequently converted in the known manner to --CONQ 1  Q 2  or --COOQ 3 . The trisaminopyridines are useful as intermediates for preparation of azo dyestuffs by coupling with diazo components in the known manner.

This is a Continuation, of Ser. No. 793,369 filed May 3, 1977 now abandoned which is a continuation of Ser. No. 496,715 filed Aug. 12, 1974 now U.S. Pat. No. 4,038,268 which in turn is a continuation-in-part of Ser. No. 442,621 filed Feb. 14, 1974 now U.S. Pat. No. 4,006,128.

This invention relates to azo dyestuffs which are free of sulphonic acid groups and carboxylic acid groups. The dyestuffs are prepared by coupling a diazotized amine of the formula

    D--NH.sub.2                                                (II)

with a coupling component (IV) which is obtained by reacting a pyridinium salt of the formula (III) below with at least two equivalents of an organic amine at a temperature of 110° to 130° C. and optionally converting the cyano group into an ester or carbonamide group in the known manner.

The reaction of the pyridinium salt (III) with the amines is either carried out in excess amine or in the presence of an inert solvent such as, for example, chloroform, acetonitrile, tetrahydrofurane and others.

The pyridinium salt has the formula ##STR3## in which R is substituted or unsubstituted alkyl, cycloalkyl, aralkyl, or aryl; and

R₁ is substituted or unsubstituted alkyl or aralkyl.

The pyridinium salts (III) are in part known from Angewandte Chemie 84, 1184 (1972) or obtainable according to the process described there.

The organic amine, for example, can have the formula

    R.sub.3 --NH.sub.2

in which

R₃ is substituted or unsubstituted alkyl, aralkyl or aryl, particularly C₁ -C₄ -alkyl which can be substituted by hydroxy, methoxy or ethoxy; benzyl or phenylethyl which can be substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; phenyl or phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano.

Suitable organic amines are primary C₁ -C₄ -alkylamines, arylamines and phenyl-C₁ -C₃ -alkylamines, such as, for example, methylamine, ethylamine, n-propylamine, n-butylamine, β-hydroxyethylamine, aniline, benzylamine, phenylethylamine, γ-hydroxypropylamine γ-ethoxypropylamine, β-methoxyethylamine and γ-methoxypropylamine.

As already indicated, the cyano group in the coupling component can be optionally converted to an ester or a carbonamide group in the known manner.

The carbonamide group can be represented by the formula ##STR4## in which Q₁ and Q₂ independently of one another are hydrogen, alkyl, cycloalkyl, aralkyl or aryl; or conjointly with the nitrogen atom form a 5-membered or 6-membered heterocyclic structure; for example a morpholine, piperidine or pyrrolidine ring.

The ester group can be represented by the formula

    --COOQ.sub.3

in which

Q₃ is alkyl or aralkyl.

Suitable radicals D in the diazotized amine (II) are aromatic-carboxylic radicals, especially those of the benzene, diphenyl, naphthalene and anthraquinone series, and aromatic-heterocyclic radicals, preferably those of the thiadiazole, triazole, benztriazole, indole, benzthiazole and oxdiazole series.

Preferred radicals D are radicals of the benzene, thiadiazole and benzthiazole series. These radicals can possess further non-ionic substituents customary in dyestuff chemistry. As examples there may be mentioned: halogen atoms, such as chlorine, bromine and fluorine, alkyl, alkoxy aryl, aryloxy, nitro, cyano, trifluoromethyl, alkylcarbonyl, alkoxycarbonyl, arylcarbonyl, alkylsulphonyl, arylsulphonyl, alkylcarbonylamino, arylcarbonylamino, arylazo, sulphamoyl and carbamoyl radicals; alkyl and alkoxy are preferably to be understood as radicals of this type with 1-4 C atoms and aryl is preferably to be understood as phenyl radicals which are optionally substituted by halogen, C₁ -C₄ -alkyl and C₁ -C₄ -alkoxy.

The alkyl radicals R, R₁, Q₁, Q₂ and Q₃ preferably possess 1-6 C atoms and can be substituted, for example, by halogen, such as F, Cl or Br, or by cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl groups.

Cycloalkyl radicals R, Q₁ and Q₂ can preferably be cyclohexyl radicals which can be substituted by, for example, methyl radicals.

Suitable aryl radicals R, Q₁ and Q₂ are above all phenyl radicals which are optionally substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano; halogen is preferably to be understood as chlorine. The phenyl and tolyl radical are preferred.

Suitable aralkyl radicals R, R₁, Q₁, Q₂ and Q₃ are preferably benzyl and phenylethyl radicals which can be substituted by, for example, chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.

Particularly valuable dyestuffs ar obtained by coupling a diazotized amine of having the formula ##STR5## in which Y is halogen, nitro, cyano, CF₃, C₂ -C₅ -alkylcarbonylamino, C₁ -C₄ -alkylsulphonyl, C₂ -C₅ -alkoxycarbonyl, phenyl, ##STR6## and Z is hydrogen, methyl, C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, nitrile or halogen;

V₁ and V₂ independently of one another are hydrogen or C₁ -C₄ -alkyl; and

n is the number 1 or 2; with a coupler (IV) prepared as indicated above in which the cyano group is unconverted or is converted to --CONQ₁ Q₂ ; and in which R and R₁ are C₁ -C₆ -alkyl, or C₁ -C₆ -alkyl substituted by OH, CN, halogen, C₁ -C₄ -alkoxy or C₂ -C₅ -alkylcarbonyl; and

Q₁ and Q₂ are hydrogen or C₁ -C₄ -alkyl.

The abovementioned C₁ -C₄ -alkyl radicals are n-propyl, n-butyl and above all methyl and ethyl radicals. Halogen is preferably to be understood as chlorine and bromine.

Among the C₂ -C₅ -alkoxycarbonyl radicals Y which have been mentioned, the methoxycarbonyl and ethoxycarbonyl radicals are to be regarded as particularly suitable. Acetyl is the preferred alkylcarbonyl group.

It has now been discovered that the reaction of an amine having the formula R₃ NH₂ with a pyridinium salt having the formula ##STR7## under the conditions described above is ##STR8## and not ##STR9## as incorrectly described in our parent application, Ser. No. 442,621.

Accordingly, the dyestuffs of this invention produced by the method described above are found to have the formula ##STR10## in which D, R and R₁ and R₃ all have the meanings given above and

X is cyano, or an ester or carbonamide group as defined above.

The coupling of the diazotized amines (II) with the compounds (IV) is carried out in a manner which is in itself known, in a weakly acid, neutral or weakly alkaline, aqueous or organic-aqueous medium, the addition of an acid-binding agent, such as, for example, sodium acetate, being advisable at times

As examples of suitable diazo compounds of the formula (II) there may be mentioned: aniline,2-, 3- and 4-N,N-dimethylamino-aniline, 2-, 3- and 4-aminotoluene, 3- and 4-amino-benzotrifluoride, 3- and 4-amino-1,2-dimethyl-benzene, 2-, 4- and 5-amino-1,3-dimethylbenzene, 4-amino-1,3,5-trimethylbenzene, 2-, 3- and 4-aminoanisole, 2-, 3- and 4-aminophenetole, 2-amino-1,4-dimethoxybenzene, 2-amino-1,4-diethoxybenzene, 2-, 3- and 4-chloroaniline, 2-, 3- and 4-bromoaniline, 2,3-, 2,4-, 2,5- and 3,4-dichloroaniline, 2,5-dibromoaniline, 2,4,5-, 2,4,6-, 3,4,5- and 3,4,6-trichloroaniline, 3-, 4-, 5- and 6-chloro-2-amino-toluene, 4-chloro-3-amino-toluene, 2-chloro-4-amino-toluene, 5-chloro-2-amino-benzotrifluoride, 4,5- and 4,6-dichloro-2-amino-toluene, 2,5- and 4,6-dichloro-3-amino-toluene, 2,5- and 3,5-dichloro-4-amino-toluene, 4,5,6-trichloro-2-amino-toluene, 4-chloro-2-amino-1,3-dimethylbenzene, 6-chloro-3-amino-anisole, 2-chloro-4-amino-anisole, 3-chloro-4-aminoanisole, 2-, 3- and 4-nitroaniline, 3-nitro-4-amino-toluene, 5-nitro-4-amino-1,3-dimethylbenzene, 6-nitro-3-amino-anisole, 3-nitro-4-amino-anisole, 5-nitro-2-aminophenetole, 2-nitro-4-amino-phenetole, 3-nitro-4-amino-phenetole, 5-nitro-2-amino-1,4-dimethoxy-benzene, 5-nitro-2-amino-1,4-diethoxy-benzene, 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, 4-chloro-2-nitroaniline, 4-bromo-2-nitroaniline, 2,6-dichloro-4-nitroaniline, 2-chloro-6-bromo-4-nitroaniline, 2,6-dibromo-4-nitroaniline, 2,4-dinitroaniline, 6-chloro-2,4-dinitroaniline, 6-bromo-2,4-dinitroaniline, 2,4,6-trinitroaniline, 2-, 3- and 4-amino-benzonitrile, 1-amino-2-cyano-5-chlorobenzene, 2-cyano-4-nitroaniline, 4-cyano-3-nitroaniline, 2,5-dichloro-4-aminosulphonylaniline, 4-methylsulphonylaniline, 1-amino-2,4-dicyanobenzene, 1-amino-2,6-dicyano-4-nitrobenzene, 1-amino-2-chloro-4-methyl-sulphonylbenzene, 2-methylsulphonyl-4-nitroaniline, 4-methylsulphonyl-2-nitroaniline, 2-, 3- and 4-amino-benzaldehyde, 2-, 3- and 4-amino-acetophenone, 2-amino-5-nitro-acetophenone, 2-, 3- and 4-amino-benzophenone, 2-, 3- and 4-amino-4'-methyl-benzophenone, 2-, 3- and 4-amino-4'-methoxy-benzophenone, 4-amino-5-nitro-benzophenone, 2-, 3- and 4-amino-benzoic acid ethyl ester, 2-, 3- and 4-aminobenzoic acid n-butyl ester, 2-, 3- and 4-amino-benzoic acid cyclohexyl ester, 2-, 3- and 4-amino-benzoic acid amide, 2-, 3- and 4-amino-benzoic acid monomethylamide, 2-, 3- and 4-amino-benzoic acid dimethylamide, 2-, 3- and 4-amino-benzoic acid ethyleneimide, 2-, 3- and 4-amino-benzoic acid isopropylamide, 2-, 3- and 4-amino-benzoic acid diethylamide, 2-, 3-and 4-amino-benzoic acid di-n-butylamide, 2-, 3- and 4-aminobenzoic acid morpholide, 2-, 3- and 4-amino-benzoic acid anilide, 2-, 3- and 4-amino-benzoic acid N-methylanilide, 2-, 3- and 4-amino-phenyl acetic acid ester, 2-, 3- and 4-aminophenyl β-methoxy-propionic acid ester, 2-, 3- and 4-aminophenyl phenylacetic acid ester, 2-, 3- and 4-amino-phenyl phenoxyacetic acid ester, 2-, 3- and 4-amino-phenyl benzoic acid ester, 2-, 3- and 4-amino-phenyl methylsulphonic acid ester, 2-, 3- and 4-amino-phenyl ethylsulphonic acid ester, 2-, 3- and 4-amino-phenyl β-chloroethylsulphonic acid ester, 2-, 3- and 4-amino-phenyl butylsulphonic acid ester, 2-, 3- and 4 -amino-phenyl n-hexylsulphonic acid ester, 2-, 3- and 4-amino-phenyl phenylsulphonic acid ester, 2-, 3- and 4-aminophenyl (4'-methyl-phenyl)-sulphonic acid ester, 2-, 3- and 4-amino-phenyl (4'-methoxy-phenyl)-sulphonic acid ester, 2-, 3- and 4-amino-phenyl β-ethoxy-ethylsulphamic acid ester, 2-, 3- and 4-amino-benzenesulphonic acid ethyl ester, 2-, 3- and 4-amino-benzenesulphonic acid phenyl ester, 2-, 3- and 4-amino-phenyl dimethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl ethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl diethylsulphamic acid ester, 2-, 3- and 4-amino-phenyl di-n-butylsulphamic acid ester, 2-, 3- and 4-amino-phenyl cyclohexylsulphamic acid ester, 2-, 3- and 4-amino-benzenesulphonic acid amide, 2-, 3- and 4-amino-benzenesulphonic acid monomethylamide, 2-, 3- and 4-aminobenzenesulphonic acid dimethylamide, 2-, 3- and 4-amino-benzenesulphonic acid ethyleneimide, 2-, 3- and 4-amino-benzenesulphonic acid diethylamide, 2-, 3- and 4-amino-benzenesulphonic acid di-n-butylamide, 2-, 3- and 4-amino-benzenesulphonic acid morpholide, 2-, 3- and 4-amino-benzenesulphonic acid cyclohexylamide, 2-, 3- and 4-amino-benzenesulphonic acid anilide, 2-, 3- and 4-amino-benzenesulphonic acid N-methyl-anilide, 1-methyl-2-amino-benzene-4-sulphonic acid amide, 1-methoxy-2-amino-benzene-4-sulphonic acid amide, 1-methoxy-2-amino-benzene-4-sulphonic acid N-methylanilide, 1-chloro-2-amino-benzene-4-sulphonic acid dimethylamide, 1-chloro-2-amino-benzene-5-sulphonic acid β-ethoxy-ethylamide, 1-chloro-3-amino-benzene-4-sulphonic acid amide, 1-chloro-4-amino-benzene-2-sulphonic acid dimethylamide, 4-amino-benzene-methylurethane, 2-, 3- and 4-amino-acetanilide, 2-, 3- and 4-amino-phenoxyacetanilide, 2-, 3- and 4-amino-N-methyl-acetanilide, 4-amino-diphenyl, 4-amino-diphenyl-4'-carboxylic acid ethyl ester, 4-amino-4'-acetylamino-diphenyl, 4-amino-2',4'-dinitro-diphenylamine, 4-amino-3-nitro-diphenylamine-4'-sulphonic acid amide, 1-aminonaphthalene, 1-amino-5-ethoxy-naphthalene, 2-chloro-1-aminonaphthalene, 2-amino-naphthalene, 2-amino-naphthalene-6-sulphonic acid dimethylamide, 5-nitro-2-amino-thiazole, 4-amino-azo-benzene, 2',3-dimethyl-4-amino-azo-benzene, 2-methyl-4-amino-5-methoxy-azo-benzene, phenyl-azo-4-aminonaphthalene, 4-methylsulphonylaniline, 2-aminothiazole, 2-amino-5-nitrothiazole, 2-amino-5-thiocyanatothiazole, 2-aminobenzthiazole, 2-amino-6-methoxybenzthiazole, 2-amino-6-ethoxybenzthiazole, 2-amino-6-chlorobenzthiazole, 2-amino-4,5-dichlorobenzthiazole, 2-amino-5,6-dichlorobenzthiazole, 3-amino-5-nitrobenzisothiazole and 3-phenyl-5-amino-thiadiazole(1,2,4).

The new dyestuffs are very suitable for dyeing and printing structures of synthetic materials such as, for example, polyolefines, polyvinyl compounds, cellulose 21/2-acetate, cellulose triacetate and especially polyester materials, for example polyethylene glycol terephthalate. On these they give, by the customary dyeing and printing processes, yellow to blue dyeings and prints with good fastness properties, especially good fastness to light and sublimation.

The materials mentioned are appropriately dyed from aqueous suspension in the presence of carriers between about 80° C. and 110° C., in the absence of carriers between about 110° C. and 140° C., or by the thermofixing process at about 170° C. and 230° C. Printing can be carried out by steaming the printed goods in the presence of a carrier at temperatures between 80° C. and 100° C. or in the absence of a carrier at about 110° C. to 140° C. or treating them by the thermofixing process at about 170° C. and 230° C.

In the examples which follow, parts denote parts by weight and percentages denote percentages by weight.

EXAMPLE 1

23.3 parts of 1-methyl-2-chloro-3-cyano-4-methylamino-6-amino-pyridinium chloride (prepared according to the instructions of A. L. Cossey; Angewandte Chemie, 84 (1972) page 1185, and 100 parts of benzylamine are heated to 110°-130° C. for four to six hours. The reaction mixture is subsequently introduced, while still hot, into approximately 500 parts of ice water. The product which precipitates is filtered off, thoroughly washed with water and dried. Approximately 24 parts of the compound of the formula ##STR11## are obtained; the compound melts, after recrystallization from ethanol, at 148°-153° C. and contains small quantities of a pyridone impurity, produced by hydrolysis.

The table which follows indicates further dyestuffs according to the present invention and the colour shades of dyeings or prints which are obtainable therewith on polyester materials and which also possess good fastness properties.

    __________________________________________________________________________      Diazotized Amine     Coupled with the reaction product of                                                                  ##STR12##                          (D-NH.sub.2)         amine (R.sub.3 NH.sub.2) reacted with                                                                 Colour shade                      No.   D                R.sub.3       R   R.sub.1                                                                           on polyester                       __________________________________________________________________________     2.  4-Chlorophenyl   CH.sub.3        CH.sub.3                                                                           CH.sub.3                                                                          yellow                             3.  2,5-Dichlorophenyl                                                                              CH.sub.3        CH.sub.3                                                                           "  yellow                             4.  4-Phenylazophenyl                                                                               C.sub.2 H.sub.5 CH.sub.3                                                                           "  orange                             5.  2,5-Dichlorophenyl                                                                              C.sub.3 H.sub.7 CH.sub.3                                                                           "  yellow                             6.  4-Phenylazophenyl                                                          n-C.sub.4 H.sub.9                                                                  CH.sub.3         "               orange                                    7.  4-Chlorophenyl   C.sub.6 H.sub.5 CH.sub.3                                                                           "  yellow                             8.  2,5-Dichlorophenyl                                                                              "               CH.sub.3                                                                           "  yellow                             9.  2-Chloro-4-nitrophenyl                                                                          "               CH.sub.3                                                                           "  orange                             10. 4-Cyanophenyl    "               CH.sub.3                                                                           "  yellow                             11. 4-Carboethoxyphenyl                                                                             "               CH.sub.3                                                                           "  yellow                             12. 4-Methylphenyl   "               CH.sub.3                                                                           "  yellow                             13. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                           "  orange                             14. 3-Chlorophenyl   CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           "  yellow                             15. 4-Chlorophenyl   "               CH.sub.3                                                                           "  yellow                             16. 3,5-Dichlorophenyl                                                                              "               CH.sub.3                                                                           "  yellow                             17. 2,4-Dichlorophenyl                                                                              "               CH.sub.3                                                                           "  yellow                             18. 3-Methylphenyl   "               CH.sub.3                                                                           "  yellow                             19  4-Methylphenyl   "               CH.sub.3                                                                           "  yellow                             20. 3-Trifluoromethylphenyl                                                                         "               CH.sub.3                                                                           "  yellow                             21. 4-Methoxyphenyl  "               CH.sub.3                                                                           "  yellow                             22. 2-Chloro-4-methylphenyl                                                                         "               CH.sub.3                                                                           "  yellow                             23. 2-Trifluoromethyl-5-chlorophenyl                                                                "               CH.sub.3                                                                           "  yellow                             24. 2-Chloro-5-methyoxphenyl                                                                        "               CH.sub.3                                                                           "  yellow                             25. 2-Chloro-4-nitrophenyl                                                                          "               CH.sub.3                                                                           "  orange                             26. 2-Cyanophenyl    "               CH.sub.3                                                                           "  yellow                             27. 4-Cyanophenyl    "               CH.sub.3                                                                           "  yellow                             28. 2-Cyano-5-chlorophenyl                                                                          "               CH.sub.3                                                                           "  yellow                             29. 2-Cyano-4-nitrophenyl                                                                           "               CH.sub.3                                                                           "  orange                             30. 2,4-Dicyanophenyl                                                                               "               CH.sub.3                                                                           "  yellow                             31. 3,4-Dicyanophenyl                                                                               "               CH.sub.3                                                                           "  yellow                             32. 4-Methylsulphonylphenyl                                                                         "               CH.sub.3                                                                           "  yellow                             33. 4-Acetylphenyl   "               CH.sub. 3                                                                          "  yellow                             34. 4-Carboethoxyphenyl                                                                             "               CH.sub.3                                                                           "  yellow                             35. 4-Acetaminophenyl                                                                               "               CH.sub.3                                                                           "  yellow                             36. 4-Carbonamidophenyl                                                                             "               CH.sub.3                                                                           "  yellow                             37. 3-Sulphonamidophenyl                                                                            "               CH.sub.3                                                                           "  yellow                             38. 4-Sulphonamidophenyl                                                                            "               CH.sub.3                                                                           "  yellow                             39. 4-Sulphamidoxyphenyl                                                                            "               CH.sub.3                                                                           "  yellow                             40. 3-Sulphamidoxyphenyl                                                                            "               CH.sub.3                                                                           "  yellow                             41. 3-N,N-diethylsulphamidoxyphenyl                                                                 "               CH.sub.3                                                                           "  yellow                             42. 3-Nitrophenyl    "               CH.sub.3                                                                           "  yellow                             43. 2-Nitro-4-cyclohexylphenyl                                                                      "               CH.sub.3                                                                           "  orange                             44. 4-Phenylaminophenyl                                                                             "               CH.sub.3                                                                           "  yellow                             45. Naphthyl-1       "               CH.sub.3                                                                           "  yellow                             46. Naphthyl-2       "               CH.sub.3                                                                           "  yellow                             47. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                           "  orange                             48. 4-Phenylazonaphthyl-1                                                                           "               CH.sub.3                                                                           "  red                                49. 5-Nitro-thiazolyl-2                                                                             "               CH.sub.3                                                                           "  red                                50. 6-Chloro-benzthiazolyl-2                                                                        "               CH.sub.3                                                                           "  red                                51. 4-Chlorophenyl   "               C.sub.2 H.sub.5                                                                    C.sub.2 H.sub.5                                                                   yellow                             52. 2,5-Dichlorophenyl                                                                              "               C.sub.2 H.sub.5                                                                    "  yellow                             53. 4-Phenylazophenyl                                                                               "               C.sub.2 H.sub.5                                                                    "  orange                             54. 2,5-Dichlorophenyl                                                                              "               C.sub.6 H.sub.5                                                                    C.sub.6 H.sub.5                                                                   yellow                             55. 4-Phenylazophenyl                                                                               "               C.sub.6 H.sub.5                                                                    "  orange                             56. 2,5-Dichlorophenyl                                                                               ##STR13##      CH.sub.3                                                                           CH.sub.3                                                                          yellow                             57. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                           "  orange                             58. "                                                                                                ##STR14##      CH.sub.3                                                                           "  orange                             59. "                                                                                                ##STR15##      CH.sub.3                                                                           "  orange                             60. 2,5-Dichlorophenyl                                                                              CH.sub.2CH.sub.2C.sub.6 H.sub.5                                                                CH.sub.3                                                                           "  yellow                             61. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                           "  orange                             62. 2,5-Dichlorophenyl                                                                              CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             63. "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  yellow                             64. "                CH.sub.2CH.sub.2CN                                                                             CH.sub.3                                                                           "  yellow                             65. "                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           C.sub.2 H.sub.5                                                                   yellow                             66. "                CH.sub.2C.sub.6 H.sub.5                                                                        C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          yellow                             67. 4-Phenylazophenyl                                                                               CH.sub.2C.sub.6 H.sub.5                                                                        C.sub.2 H.sub.5                                                                    "  orange                             68. 2,5-Dichlorophenyl                                                                              C.sub.6 H.sub.5 C.sub.2 H.sub.5                                                                    CH.sub.3                                                                          yellow                             69. "                C.sub.6 H.sub.5 C.sub.6 H.sub.5                                                                    C.sub.6 H.sub.5                                                                   yellow                             70. "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           C.sub.6 H.sub.5                                                                   yellow                             71. 4-Phenylazophenyl                                                                               "               CH.sub.3                                                                           "  orange                             72. "                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           CH.sub.3                                                                          orange                             73. 2-Chloro-5-trifluoromethylphenyl                                                                CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           CH.sub.3                                                                          yellow                             74. 4-Cyclohexyloxycarbonylphenyl                                                                   "               CH.sub.3                                                                           "  yellow                             75. 2-Nitrophenyl    "               CH.sub.3                                                                           "  scarlet                            76. "                "               CH.sub.3                                                                           "  scarlet                            77. 2-Chloro-4-nitrophenyl                                                                          "               CH.sub.3                                                                           "  scarlet                            78. 2-Methoxy-4-nitrophenyl                                                                         "               CH.sub.3                                                                           "  red                                79. 2-Cyano-4-nitrophenyl                                                                           "               CH.sub.3                                                                           "  red                                80. 2-Methylsulphonyl-4-nitrophenyl                                                                 "               CH.sub.3                                                                           "  red                                81. 2-Carbomethoxy-4-nitrophenyl                                                                    "               CH.sub.3                                                                           "  red                                82. 2,5-Dimethoxy-4-nitrophenyl                                                                     "               CH.sub.3                                                                           "  red                                83. Thiazolyl-2      "               CH.sub.3                                                                           "  orange                             84. 6-Methoxybenzthiazolyl-2                                                                        "               CH.sub.3                                                                           "  scarlet                            85. 5,6-dichlorobenzthiazolyl-2                                                                     "               CH.sub.3                                                                           "  scarlet                            86. 2-Cyanophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub. 3                                                                          "  yellow                             87. "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  yellow                             88. "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             89. "                CH.sub.2CH.sub.2CH.sub.OCH.sub.3                                                               CH.sub.3                                                                           "  yellow                             90. 4-Methylsulphonylphenyl                                                                         CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             91. "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  yellow                             92. "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             93. "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  yellow                             94. "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  yellow                             95. "                                                                                                ##STR16##      CH.sub.3                                                                           "  yellow                             96. 4-Sulphonamidophenyl                                                                            CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             97. 4-Sulphonamidophenyl                                                                            CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.2                                                                           "  yellow                             98. "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             99. "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  yellow                             100.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  yellow                             101.                                                                               2,5-Dichloro-4-sulphonamidophenyl                                                               CH.sub.2C.sub.6 H.sub.5                                                                        CH.sub.3                                                                           "  golden yellow                      102.                                                                               "                CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  golden yellow                      103.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  golden yellow                      104.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  golden yellow                      105.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  golden yellow                      106.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  golden yellow                      107.                                                                               2,5-Dichloro-4-benzylamino-                                                                     CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  golden yellow                          sulphonylphenyl                                                            108.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  golden yellow                      109.                                                                               2-Chloro-5-trifluoromethylphenyl                                                                CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             110.                                                                               "                CH.sub.2 CH.sub.2OCH.sub.3                                                                     CH.sub.3                                                                           "  yellow                             111.                                                                               "                                                                                                ##STR17##      CH.sub.3                                                                           "  yellow                             112.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             113.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  yellow                             114.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  yellow                             115.                                                                               4-Cyclohexyloxycarbonylphenyl                                                                   CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             116.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  yellow                             117.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             118.                                                                               "                                                                                                ##STR18##      CH.sub.3                                                                           "  yellow                             119.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  yellow                             120.                                                                               2-Nitrophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  scarlet                            121.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  scarlet                            122.                                                                               "                CH.sub.2 CH.sub.2CH.sub.2OCH.sub.3                                                             CH.sub.3                                                                           "  scarlet                            123.                                                                               3-Nitrophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             124.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             125.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  yellow                             126.                                                                               "                                                                                                ##STR19##      CH.sub.3                                                                           "  yellow                             127.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  yellow                             128.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  yellow                             129.                                                                               4-Nitrophenyl    CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  scarlet                            130.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  scarlet                            131.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  scarlet                            132.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  scarlet                            133.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  scarlet                            134.                                                                               2-Trifluoromethyl-4-chlorophenyl                                                                 CH.sub.2C.sub.6 H.sub.5                                                                       CH.sub.3                                                                           "  yellow                             135.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             136.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  yellow                             137.                                                                               2-Cyano-5-chlorophenyl                                                                          CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  yellow                             138.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  yellow                             139.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  yellow                             140.                                                                               "                                                                                                ##STR20##      CH.sub.3                                                                           "  yellow                             141.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  yellow                             142 2-Chloro-4-nitrophenyl                                                                          CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  scarlet                            143.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  scarlet                            144.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  scarlet                            145.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  scarlet                            146.                                                                               "                CH.sub.2CH.sub.2CH.sub.2 OC.sub.2 H.sub.5                                                      CH.sub.3                                                                           "  scarlet                            147.                                                                               2-Methoxy-4-nitrophenyl                                                                         CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  red                                148.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  red                                149.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  red                                150.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  red                                151.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  red                                152.                                                                               2-Cyano-4-nitrophenyl                                                                           CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  red                                153.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  red                                154.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  red                                155.                                                                               "                                                                                                ##STR21##      CH.sub.3                                                                           "  red                                156.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  red                                157.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  red                                158.                                                                               2-Methylsulphonyl-4-nitrophenyl                                                                  CH.sub.2CH.sub.2OH                                                                            CH.sub.3                                                                           "  red                                158.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  red                                159.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  red                                160.                                                                               "                                                                                                ##STR22##      CH.sub.3                                                                           "  red                                161.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  red                                162.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  red                                163.                                                                               2,5-Dimethoxy-4-nitrophenyl                                                                     CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  red                                164.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  red                                165.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  red                                166.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  red                                167.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  red                                168.                                                                               2,5-Diethoxy-4-nitrophenyl                                                                      CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  red                                169.                                                                               "                CH.sub. 2CH.sub.2OCH.sub.3                                                                     CH.sub.3                                                                           "  red                                170.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  red                                171.                                                                               2-Carbomethoxy-4-nitrolphenyl                                                                   CH.sub.2CH.sub.2 OH                                                                            CH.sub.3                                                                           "  red                                172.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  red                                173.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  red                                174.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  red                                175.                                                                               6-Methoxybenzthiazolyl-2                                                                        CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  scarlet                            176.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  scarlet                            177.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  scarlet                            178.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  scarlet                            179.                                                                               6-Ethoxybenzthiazolyl-2                                                                         CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  scarlet                            180.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  scarlet                            181 5,6-Dichlorobenthiazolyl-2                                                                      CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  orange                             182.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  orange                             183.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  orange                             184.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  orange                             185.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  orange                             186.                                                                               5-Nitro-2,1-benzisothiazolyl-3                                                                  CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  blue                               187.                                                                               "                CH.sub.2CH.sub.2OCH.sub.3                                                                      CH.sub.3                                                                           "  blue                               188.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  blue                               189.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  blue                               190.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OC.sub.2 H.sub.5                                                       CH.sub.3                                                                           "  blue                               191.                                                                               1,3-Thiazolyl-2  CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  orange                             192.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  orange                             194.                                                                               3-Phenyl-1,2,4-thiadiazolyl-5                                                                   CH.sub.2CH.sub.2OH                                                                             CH.sub.3                                                                           "  orange                             195.                                                                               "                CH.sub. 2CH.sub.2OCH.sub.3                                                                     CH.sub.3                                                                           "  orange                             196.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OCH.sub.3                                                              CH.sub.3                                                                           "  orange                             197.                                                                               "                CH.sub.2CH.sub.2CH.sub.2OH                                                                     CH.sub.3                                                                           "  orange                             __________________________________________________________________________

If instead of the 3-cyanopyridine derivatives corresponding compounds substituted in the 3-position by carbonamide or carboxylic acid ester groups are used as coupling components, corresponding diazo components give dyestuffs which dye polyester materials in similar color and with similar fastness properties. 

We claim:
 1. A compound of the formula ##STR23## in which X is --CN;R is C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted by halogen, CN, OH, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; cyclohexyl; methylcyclohexyl; phenyl; phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano; benzyl; phenethyl; or benzyl or phenethyl substituted with chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; R₁ is C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted with halogen, cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; benzyl, phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; and R₃ is C₁ -C₄ -alkyl; C₁ -C₄ -alkyl substituted by hydroxy, methoxy or ethoxy; benzyl; phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; phenyl; or phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano.
 2. A process for the preparation of a compound of the formula ##STR24## by reacting a pyridinium salt of the formula ##STR25## with at least two equivalents of an organic amine of the formula R₃ NH₂ at a temperature of 110° to 130° C.; in whichR is C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted by halogen, CN, OH, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; cyclohexyl; methylcyclohexyl; phenyl; phenyl substituted by C₁ -C₄ -alkoxy, halogen or cyano; benzyl; phenethyl; or benzyl or phenethyl substituted with chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; R₁ is C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted with halogen, cyano, hydroxyl, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; benzyl; phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; and R₃ is C₁ -C₄ -alkyl; C₁ -C₄ -alkyl substituted by hydroxy, methoxy or ethoxy; benzyl; phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy; phenyl; or phenyl substituted by C₁ -C₄ -alkyl, C₁ -C₄ -alkoxy, halogen or cyano.
 3. The compound of claim 1 in whichR and R₁ are identical and are C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted with halogen, cyano, C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; benzyl, phenethyl; benzyl or phenethyl substituted by chlorine C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy.
 4. The process of claim 2 in whichR and R₁ are identical and are C₁ -C₆ -alkyl; C₁ -C₆ -alkyl substituted with halogen, cyano C₁ -C₄ -alkoxy or C₂ -C₅ -alkoxycarbonyl; benzyl, phenethyl; benzyl or phenethyl substituted by chlorine, C₁ -C₄ -alkyl or C₁ -C₄ -alkoxy. 